Lightweight, Durable Apparel and Laminates for Making the Same

ABSTRACT

Laminates are described having a durable outer film surface for use in making lightweight liquidproof articles, including articles of apparel, such as outerwear garments. A method of making the laminate and a lightweight outerwear garment having an abrasion resistant exterior film surface is described.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.12/539,234, filed Aug. 11, 2009, which is a continuation-in-part of U.S.patent application Ser. No. 12/465,383, filed May 13, 2009.

FIELD OF THE INVENTION

Described herein is a breathable lightweight durable laminate having anouter film surface, and a lightweight durable article of apparel madefrom the laminate having an exterior film surface.

BACKGROUND OF THE INVENTION

Articles of apparel having film layers for providing water resistance orliquidproofness, while simultaneously providing breathability are known.Laminates and garments are constructed to provide protection to the filmlayer so as to resist tearing, damage by puncture or abrasion, and thelike. Inner and outer fabric layers are most frequently added to bothsurfaces of the film to protect the film surface from damage.

Alternatively, garments having a film surface uncovered by a protectiveinner or outer layer of fabric are often constructed for use incombination with another garment whose fabric surface will provideprotection to the film layer against damage. For example, anundergarment comprising a film composite lacking an outer protectivefabric layer is constructed to be used under a separate outer garmentwhere it is less susceptible to sustaining direct damage.

The addition of outer and inner fabric layers required to protect filmlayers from damage adds weight to an article of apparel, and results inmaterials having a higher water pickup on the outer surface. Moreover,wearing an outerwear garment to protect an undergarment having a filmlayer forms a bulky ensemble.

SUMMARY OF THE INVENTION

A lightweight laminate having an outer film surface is described. Thelightweight laminate is sufficiently durable against abrasion for use inmaking articles of apparel and other articles, such as outerweargarments and shelters, having an exterior film surface that remainsliquidproof after an abrasion challenge. The lightweight laminate has aporous polymer surface that can be colorized, for example, by printing.The laminate outer film surface can be coated with a hydrophobic andoleophobic coating composition to provide oleophobicity and aid in theretention of waterproofness or water resistance.

A method of making a lightweight laminate having an abrasion resistantouter film surface is described. The method comprises the steps ofselecting a textile layer; selecting a rugged porous fluoropolymermembrane; coating and colorizing the porous fluoropolymer membrane toform a hydrophobic and oleophobic fluoropolymer film having an outerfilm surface; and laminating the textile and the porous fluoropolymerfilm to form a laminate, optionally before or after the coating step orthe colorizing step, to form a laminate having an outer film surface andan inner textile surface. In one embodiment, a laminate is formed havinga moisture vapor transmission rate that is greater than 1000 g/m²/24hours, a laminate mass per area less than 200 g/m², and the laminateouter film surface that is abrasion resistant, resulting in a durablyliquidproof laminate.

A method of making an article of apparel, such as a lightweightouterwear garment, having an abrasion resistant durably liquidproofexterior film surface is described. The method comprises the steps ofselecting a laminate having a woven, knit, or non-woven textile layerlaminated to a porous fluoropolymer membrane; coating and colorizing theporous fluoropolymer membrane with an oleophobic polymer composition,optionally before or after the laminating step, thereby forming alaminate having an outer film surface and an inner textile surface;assembling an outerwear garment from the laminate so that the colorizedouter film surface is the outerwear garment exterior film surface andthe textile inner surface is on a side opposite the outer film surface.

DESCRIPTION OF THE DRAWINGS

The operation of the present invention should become apparent from thefollowing description when considered in conjunction with theaccompanying drawings, in which:

FIG. 1 a is perspective view of one embodiment of a garment frontsurface.

FIG. 1 b is perspective view of one embodiment of a garment backsurface.

FIG. 2 is a perspective view of one embodiment of a laminate.

FIG. 3 a is a micrograph of a cross-sectional view of a sample of thehook material used in the Hook Modified Abrasion Test.

FIG. 3 b is a micrograph of a top-down surface view of a sample of thehook material used in the Hook Modified Abrasion Test

DETAILED DESCRIPTION OF THE INVENTION

Described, herein, is a breathable lightweight, durable laminate for usein making liquidproof articles of apparel having low water pick-up, suchas outerwear garments. The laminate is designed having a durablycolorized outer film surface. A breathable lightweight, outerweargarment is described that comprises an exterior film surface that isresistant to abrasion and is therefore durably liquidproof, and has aprintable non-textile exterior surface.

One embodiment, exemplified in FIGS. 1 a and 1 b, illustrates aperspective view of a garment (1) in the form of a jacket having agarment exterior non-textile surface on the garment front surface (20)and the garment back surface (21). The jacket (1) comprises an exteriornon-textile surface (2) and an interior textile surface (3) that facestowards the body of a wearer. The jacket (1) comprises a front closure(4), sleeves (5) with wrist cuffs (6), and a waist band (7). The garmentis formed from a laminate, exemplified in the cross-sectionalillustration of FIG. 2. In one embodiment, the garment comprises alaminate (10) that comprises an outer film surface (11) and an innertextile surface (12). The laminate (10) comprises a porous membrane (13)adjacent to a textile layer (14). The porous membrane (13) may becolorized with a colorant (16) and/or coated with an oleophobiccomposition that is also hydrophobic, forming the outer film surface(11) of the laminate (10). The textile layer (14) is adjacent to theporous membrane (13) on a side opposite the outer film surface (11) andis attached to the porous membrane by attachments (15), which areexemplified in FIG. 2 as discontinuous attachments.

It is desirable to make laminates having a film surface that can bedurably coated, for example with colorants and oleophobic coatings.Where the membrane layer is a low surface energy film, such as manyfluoropolymer materials, membrane porosity is helpful to achieve durablemechanical bonding of the coating compositions within the membranestructure. However, many porous films are known to abrade easily makingit difficult to achieve durable liquidproofness when using the porousfilms in applications that will subject them to abrasion. Laminatesdescribed herein have a film surface formed from membranes havingsufficient porosity to provide a durable coating but that are resistantto abrasion maintaining liquidproofness.

The outer porous film surface (11) of the laminate (10) can be made, forexample, from a porous membrane comprising polymeric materials such asfluoropolymers, polyolefins, polyurethanes, and polyesters. Suitablepolymers may comprise resins that can be processed to form porous ormicroporous membrane structures. For example, polytetrafluoroethylene(PTFE) resins that can be processed to form stretched porous structuresare suitable for use herein. For example, PTFE resins can be stretchedto form microporous membrane structures characterized by nodesinterconnected by fibrils when expanded according to the process taughtin patents such as in U.S. Pat. No. 3,953,566, 5,814,405, or 7,306,729.In some embodiments, expanded PTFE fluoropolymer films are made fromPTFE resins according to U.S. Pat. No. 6,541,589, having comonomer unitsof polyfluorobutylethylene (PFBE). For example, microporous expandedPTFE (ePTFE) fluoropolymers can comprise PTFE having from about 0.05% byweight to about 0.5% by weight of comonomer units of PFBE based upon thetotal polymer weight.

In one embodiment, the outer porous membrane (13) comprises ePTFE havinga microstructure characterized by nodes interconnected by fibrils,wherein the pores of the porous film are sufficiently tight so as toprovide liquidproofness and sufficiently open to provide properties suchas moisture vapor transmission, and penetration by coatings of colorantsand oleophobic compositions. For example, in some embodiments, it isdesirable for the porous membranes to have a mean flow pore size of lessthan or equal to about 400 nm to provide water resistance, and a meanflow pore size greater than about 50 nm for colorization. This may beaccomplished by compounding a PTFE resin which is suited to produce anode and fibril microstructure upon stretching. The resin can be blendedwith an aliphatic hydrocarbon lubricant extrusion aid such as a mineralspirit. The compounded resin may be formed into a cylindrical pellet andpaste extruded by known procedures into a desired extrudable shape,preferably a tape or membrane. The article can be calendered to thedesired thickness between rolls and then thermally dried to remove thelubricant. The dried article is expanded by stretching in the machineand/or transverse directions, for example, according to the teachings ofU.S. Pat. No. 3,953,566, 5,814,405, or 7,406,729, to produce an expandedPTFE structure characterized by a series of nodes which areinterconnected by fibrils. The ePTFE article is then amorphously lockedby heating the article above the crystalline melt point of PTFE, forexample between about 343° C.-375° C. or between about 325° C.-390° C.

Porous polymer films may be selected that have a range of mass per areaand thickness depending on the application. For example, porous polymermembranes may be selected that have a mass per area less than about 80g/m². It may also be desirable that the porous membranes has a mass perarea greater than about 10 g/m², or greater than 18 g/m². In someembodiments it may be desirable to select a porous membranes having amass per area of less than about 60 g/m² or less than about 50 g/m² orless than about 30 g/m². It may also be desirable to select a porousmembranes that has a mass per area of between about 19 g/m² and 60 g/m².However, for applications such as footwear, it may be desirable to usemembranes having greater mass per area. Porous polymer membranes may beselected having a variety of thicknesses; in some embodiments it may bedesired that the porous polymer membranes have a thickness less thanabout 120 μm. It may further be desired that the porous polymermembranes have a thickness less than 35 μm.

Where laminates are described as durably liquidproof, it is meant thatthe laminate remains liquidproof after an abrasion challenge accordingto the Liquidproof After Abrasion test method described herein. In someembodiments, laminates that achieve durable liquidproofness comprise atextile laminated to a porous membrane that has a ball burst loadgreater than 17 lb_(f), or greater than about 19 lb_(f), when measuredaccording to the Ball Burst load test described herein. In someembodiments, laminates that achieve good durable liquidproofnesscomprise a textile laminated to a porous membrane having certainproperties when tested according to the Toughness, Maximum Load, MTS,and Modulus test described herein. For example, in some embodiments,laminates having a textile laminated to a porous membrane with anaverage maximum load (the average of the maximum load in thelongitudinal and transverse directions) greater than 10N, or greaterthan 12N, or greater than 20N, are durably liquidproof. Suitable porousmembranes may have an average modulus in the transverse and longitudinaldirection of greater than about 40 MPa or greater than about 50 MPa, orgreater than about 60 MPa. In some embodiments, durably liquidprooflaminates comprise porous membranes having an average matrix tensilestrength in the longitudinal and transverse direction of greater than 90MPa, or greater than 95 MPa, or greater than 100 MPa, or greater than150 MPa.

The porous node and fibril structure of an expanded fluoropolymermembrane enables coating materials and/or print materials to penetrateinto the porous node and fibril structure and thereby be retained in andon this expanded fluoropolymer membrane. Low surface energyfluoropolymer films, such as ePTFE, is known to repel most surfacetreatments, thereby providing a challenge for applying durable coatings,such as those comprising colorants. However, in one embodiment, acoating composition comprises a binder and a colorant to colorize a filmsurface that is used as the outer film surface of the laminate. Thecoating composition coats or encapsulates the nodes and/or fibrils ofthe expanded fluoropolymer structure forming a durable aestheticappearance.

Membranes suitable for use as the outer film surface have a surface thatwhen printed provides a durable aesthetic. Aesthetic durability can beachieved in some embodiments with colorant coating compositions thatcomprise a pigment having a particle size sufficiently small to fitwithin the pores of the porous substrate. Pigment particles having amean diameter of less than about 250 nm are useful for forming durablecolor. Coating compositions may further comprise a binder capable ofwetting the porous substrate and binding the pigment to the pore walls.

Multiple colors can be applied using multiple pigments, or varying theconcentrations of one or more pigments, or by both techniques. In oneembodiment, a laminate comprises an outer film surface and is colorizedon more than 90% of the outer film surface by printing or otherapplication technique, while retaining porosity and moisture vaportransmission. In one embodiment, the surface of the film can becolorized with a colorant to form a solid color or a pattern (design).Coating compositions comprising colorants can be applied to provide avariety of colors and designs, such as solid, camouflage and printpatterns. Coating compositions may comprise one or more colorantssuitable for use in printing camouflage patterns such as woodland anddesert patterns. In one embodiment, a coating composition suitable foruse in printing a woodlands camouflage pattern on to a surface of aporous film comprises black, brown, green, and light green colorant. Inan alternate embodiment a coating composition comprises brown, khaki,and a tan colorant suitable for printing a desert camouflage pattern.Other embodiments comprise compositions comprising colorants havingshade variations within these two examples.

The coating composition can be applied to the porous membrane, formingthe porous outer film, by several methods. Application methods forcolorizing include but are not limited to transfer coating, screenprinting, gravure printing, ink-jet printing, and knife coating.Additional topical treatments can be applied to the porous membrane,provided sufficient porosity throughout the laminate is maintained toremain moisture vapor transmissive. Additional treatments may beprovided that impart functionality, such as but not limited tooleophobicity and hydrophobicity, where a film surface lacks a desiredlevel of oleophobicity, and hydrophobicity. Examples of oleophobiccoatings include for example, fluoropolymers such as fluoroacrylates andother materials such as those taught in U.S. patent application Ser. No.11/440,870. Oleophobicity can also be provided by coating at least onesurface of the porous membrane that forms the porous outer film with acontinuous coating of an oleophobic, moisture vapor transmissivepolymer. Some examples of moisture vapor transmissive polyurethanessuitable for this application are described in U.S. Pat. No. 4,969,998.While some polymers form an outer film surface having a desirably highlevel of oleophobicity, other polymer film surfaces are insufficientlyoleophobic. The oleophobicity of these films may be increased throughthe addition of an oleophobic coating. Laminates are formed having anouter film surface with an oil rating greater than about 2 when testedaccording to the Oil Repellency Test described herein. In otherembodiments, laminates may be formed wherein the outer film surface hasan oil rating greater than or equal to about 4, or greater or equal toabout 5, or greater or equal to about 6. Optionally, the outer porousfilm may comprise a discontinuous coating, for example, in the form ofparticulates or discrete elements to provide even further abrasionresistance. A coating of discrete materials may be sprayed or coated onthe outer film surface, and may comprise, for example, polyurethane,epoxy, silicone, fluoropolymers and the like, for improving abrasionresistance of the laminate.

An aesthetically durable colorized film surface can be formed having acolor change of less than 20 Delta-E (dE) when abrasion tested on thecolorized outer film surface of the laminate according to the ColorChange After Abrasion test described herein. Laminates can also beformed having an aesthetically durable film surface having a dE lessthan 15, or a dE less than 10.

The laminate further comprises a textile (14), such as a woven, knit, ornon-woven textile, bonded to the porous outer film (13) of the laminate(10) on a side opposite the outer film surface (11). The textile (14)can be selected to provide dimensional stability to the porous outerfilm (13) when formed as a laminate. In the case of a garment, thetextile (14) may also be selected to provide a comfortable feel on theside of the laminate oriented towards the wearer. Suitable lightweighttextiles may comprise materials such as cotton, rayon, nylon andpolyester, and blends thereof. In certain applications it may bedesirable that the textile is fire resistant, and therefore maycomprise, for example, one or more materials such as aramid (e.g. soldunder the tradename Nomex or Defender), modacrylic, and fiberglass, andthe like. In some applications it may be desirable to use a textilehaving a weight of less than about 10 oz/yd², or less than about 8oz/yd², or less than about 6 oz/yd², or less than about 5 oz/yd², orless than about 3 oz/yd².

Coatings can also be provided to the textile (14) layer to impart avariety of properties to the laminate. For example, a colorant can beapplied to the textile to colorize the layer in a solid or patternedcolor having one or more than one color. The textile and the membranemaking up the outer film surface can be colorized by the same ordifferent technique, and by the same or different color or pattern, asthe outer film.

The porous membrane (13) layer forming the outer film surface (11) andthe textile (14) are bonded together in a manner that maintains adesirably high level of moisture vapor transmission. In someembodiments, for example, to maximize air permeability and moisturevapor transmission rates, discontinuous adhesive attachments are used tojoin the layers. In other embodiments, the porous membrane (13) and thetextile (14) can be laminated with a continuous adhesive, though it isdesirable that the continuous adhesive layer is moisture vaporpermeable, such as that described in U.S. Pat. No. 4,925,732, and thelaminate has a moisture vapor transmission rate greater than about 2000g/m²/24 hours. Adhesive compositions include thermoset adhesives, suchas polyurethane, and silicone. Thermoplastic adhesives includethermoplastic polyurethane. The porous membrane layer and the textileare attached by adhesive attachment through lamination processes, suchas gravure lamination, spray adhesive bonding, and fusion bonding with athermoplastic scrim to form the lightweight laminate.

Durably liquidproof laminates are abrasion resistant and do not leakafter abrasion testing on the outer film surface of the laminate forgreater than or equal to about 1400 abrasion movements when testedaccording to the Liquidproof (Suter) After Hook Abrasion test describedherein. In other embodiments laminates are formed that remainliquidproof after 3000 abrasion movements on the outer film surface.Laminates may also be formed that remain liquidproof after more than4000 abrasion movements on the outer film surface, or remain liquidprooffor more than 6000 abrasion movements on the outer film surface.

Moisture vapor transmission, or breathability, is important to providecooling to a wearer of the outerwear apparel made from laminatesdescribed herein. Laminates described herein, are therefore breathable,having a moisture vapor transmission rate (MVTR) greater than 1000g/m²/24 hours, or greater than 2000 g/m²/24 hours, or greater than 4000g/m²/24 hours, or greater than 5000 g/m²/24 hours, or greater than 10000g/m²/24 hours, or greater than 15000 g/m²/24 hours, or greater than20000 g/m²/24 hours, when tested according to the method described.Lightweight laminates described herein can be formed having a mass perarea less than about 400 g/m², or mass per area less than about 350g/m², or a mass per area less than about 200 g/m², or less than about150 g/m², or less than about 145 g/m², or less than about 125 g/m², orless than about 100 g/m².

Laminates described herein having an outer film surface have low waterpickup when compared, for example, to liquidproof laminates having anouter textile surface. In some embodiments the laminates describedherein have a water pickup less than or equal to about 10 g/m² whentested according to the Water Pickup test described herein. In otherembodiments, laminates are formed having a water pickup of less than orequal to about 8 g/m², or less than or equal to about 6 g/m², or lessthan or equal to about 4 g/m², or less than or equal to about 3 g/m².

A method is described for making lightweight laminates having anabrasion resistant outer film surface. The method comprises the steps ofselecting a textile layer; selecting a porous fluoropolymer membranehaving, for example, an average maximum load in the transverse andlongitudinal direction of greater than 10 N; and coating and/orcolorizing the porous fluoropolymer membrane with an oleophobic polymercomposition and/or a colorant to obtain a porous fluoropolymer filmhaving an oleophobic colorized outer film surface with an oil ratinggreater than 2. The method further comprises laminating the textile andthe porous fluoropolymer film to form a laminate, optionally before orafter the coating step and/or the colorizing step to form a laminatehaving an outer film surface and an inner textile surface. In oneembodiment, the laminate has a moisture vapor transmission rate greaterthan 1000 g/m²/24 hours, a mass per area less than 150 g/m², and thelaminate outer film surface is abrasion resistant, remaining liquidproofafter abrasion when abraded on the outer film surface.

A method is also described for making lightweight articles of apparelsuch as, an outerwear garment, having an abrasion resistant exteriorfilm surface. The method comprises the steps of: selecting a textilelayer and a porous fluoropolymer membrane; and coating and/or colorizingthe porous fluoropolymer membrane with an oleophobic polymer compositionand/or a colorant to obtain an oleophobic colorized outer film surfacewith an oil rating greater than 2. The method further compriseslaminating the textile and the porous fluoropolymer, optionally beforeor after the coating step and/or the colorizing step, and forming alaminate having an outer film surface and an inner textile surface thatis opposite the outer film surface, wherein the laminate has a moisturevapor transmission rate greater than 1000 g/m²/24 hours, and thelaminate is abrasion resistant and durably liquidproof after abrasiontesting on the outer film surface. The method further comprises thesteps of assembling an outerwear garment from the laminate so that thecolorized outer film surface is the outerwear garment exterior filmsurface.

Constructs made with the above described laminates include apparel suchas outerwear garments that include jackets, ponchos, raincoats, hats,hoods, gloves, pants, coveralls, footwear and the like, as well as otherarticles, such as shelters, tents, enclosures, and the like.

Test Methods Mass Per Area

The mass per area of samples is measured according to the ASTM D 3776(Standard Test Methods for Mass Per Unit Area (Weight) of Fabric) testmethod (Option C) using a Mettler-Toledo Scale, Model 1060. The scale isrecalibrated prior to weighing specimens. Weights are recorded in ouncesto the nearest half ounce. This value was converted to grams per squaremeter as reported herein.

Density for Membranes

To measure the density of the membrane material examples of the presentinvention and the comparative examples, property data measured on thesamples were collected. As noted above, the 165 mm×15 mm samples weremeasured to determine their mass (using a Mettler-Toledo analyticalbalance model AB104) and their thickness (using a Kafer FZ1000/30 snapgauge). Using this data, a density can be calculated with the followingformula:

$\rho = \frac{m}{w*l*t}$

-   -   where:        -   ρ=density (g/cc)        -   m=mass (g)        -   w=width (1.5 cm)        -   l=length (16.5 cm)        -   t=thickness (cm)

Thickness for Membranes

To measure the thickness of the membrane material examples of thepresent invention, a snap gauge (Kafer FZ1000/30) was used. Measurementswere taken in at least four areas of each sample. The average value ofthese multiple measurements is reported as the thickness value for eachmembrane.

Gurley Air Flow

The air permeability of each sample was determined based on the timerequired to pass 50 cc of air through the sample according toFED-STD-191A Method 5452 with the following exception. This test methodswas followed except that specimens were sealed prior to testing toensure a good seal and no leakage around edges during the test.

Mean Flow Pore Size Test

The Mean Flow Pore size (MFP) of the porous membrane sample was measuredaccording to ASTM F316-03 Test Method B except that silicone oil (DowCorning 200(R) fluid, 10cs) was used as the wetting fluid instead ofmineral oil. The silicone oil having a surface tension of about 20.1dynes/cm was used for samples comprising polytetrafluoroethylene (PTFE).The MFP was determined based on this test method and using a PMI ModelCFP-1500-A capillary porometer.

Ball Burst Strength

The test method and related sample mounting apparatus were developed byW. L. Gore & Associates, Inc. for use with a Chatillon Test Stand. Thetest measures the burst strength of materials such as fabrics (woven,knit, nonwoven, etc.), porous or nonporous plastic films, membranes,sheets, etc., laminates thereof, and other materials in planar form.

A specimen was mounted taut, but unstretched, between two annularclamping plates with an opening of 7.62 cm diameter. A metal rod havinga polished steel 2.54 cm diameter ball-shaped tip applied a load againstthe center of the specimen in the Z-direction (normal to the X-Y planardirections). The rod was connected at its other end to an appropriateChatillon force gauge mounted in a Chatillon Materials Test Stand, ModelNo. TCD-200. The load was applied at the rate of 25.4 cm/minute untilfailure of the specimen occurred. The failure (tearing, burst, etc.) mayoccur anywhere within the clamped area. Results were reported as theaverage of three measurements of the maximum applied force beforefailure.

Testing was done at ambient interior temperature and humidityconditions, generally at a temperature of 21° C. to 24° C. and relativehumidity of 35% to 55%. Ball burst data can be expressed as the ballburst strength as a function of mass per area of the sample; mass perarea of the sample can be determined from the product of density andthickness of the sample.

Toughness, Maximum Load, MTS, and Modulus Test Method

Sample preparation was accomplished by using a die punch to cut 165 mmlong by 15 mm wide rectangular samples out of the ePTFE membrane web.The membrane web was placed on the cutting table such that it was freefrom wrinkles in the area where the sample was to be cut. The 165 mm×15mm die was then placed on the membrane (generally in the center 200 mmof the web) such that its long axis is parallel to the direction thatwill be tested. The directions quoted in this publication will bemeasured in the longitudinal direction (parallel to the direction oftravel during processing) and the transverse direction (perpendicular tothe direction of travel during processing). Once the die is aligned,pressure is applied to it to cut through the membrane web. Upon removalof this pressure, the rectangular sample for testing should be inspectedto ensure it is free from edge defects which may impact the tensiletesting.

At least 3 samples in the longitudinal (L) and in the transverse (T)directions should be cut to characterize the membrane web. Once sampleshave been prepared, they were measured to determine their mass (using aMettler-Toledo analytical balance model AB104) and their thickness(using a Kafer FZ1000/30 snap gauge). Each sample was subsequentlytested to determine its tensile properties using an Instron 5500 tensiletester running Merlin Series IX software (version 7.51). The sampleswere inserted into the tensile tester and held using Instron Catalog2702-015 (rubber coated face plate) and 2702-016 (serrated face plate)grip plates such that each end of the sample is held between one rubbercoated and one serrated face plate. The pressure applied to the gripplates was approximately 50 psi. The gauge length between the grips wasset at 50 mm and the crosshead speed (pulling speed) was set to a speedof 508 mm/min. A 0.1 kN load cell was used to carry out thesemeasurements and data was collected at a rate of 50 points/sec. Thelaboratory temperature should be between 68° F. and 72° F. to ensurecomparable results. Finally, if the sample happened to break at the gripinterface, the data was discarded.

At least 3 samples in the longitudinal and transverse directions shouldbe successfully pulled (no slipping out of or breaking at the grips) inorder to characterize the membrane web. The data analysis andcalculations were performed with the Merlin software or any other dataanalysis package. First, the maximum load able to be supported by thesample during the tensile test for L and T directions was located. Themaximum load for L and T was then normalized to the sample physicalproperties (thickness and density) via the following equation tocalculate the matrix tensile strength for L and T directions.

${MTS} = {F_{\max}*\left( \frac{\rho_{o}*l}{100*m} \right)}$

where:

MTS=Matrix tensile strength (MTS) in Mpa

F_(max)=maximum load measured during test (Newtons)

ρ_(o)=theoretical density for PTFE (2.2 grams/cc)

l=sample length (cm)

m=sample mass (grams)

Then, the average maximum load was calculated by averaging the maximumload for L with the maximum load for T. The average matrix tensilestrength was calculated by averaging the matrix tensile for L with thematrix tensile strength for T.

The toughness for each sample was determined by integrating the stressstrain curve from the sample to calculate the area below the curve, andaveraged for three measurements for each of the L and T directions. Thisnumber represents the energy required to break the sample, reported asthe sample toughness. Then, the average toughness was calculated byaveraging the toughness L with the toughness for T.

The modulus of each sample is determined by taking the slope from thelinear elastic portion of the stress-strain curve. First, the modulus inthe longitudinal (L) and transverse (T) directions are calculated fromthe average of three measurements. Then, the average modulus iscalculated by averaging the modulus of L with the modulus of T.

Oil Repellency Test

In these tests, oil rating was measured using the AATCC Test Method118-1983 when testing the outer most film side of laminate samples.Three drops of the test oil are placed on the sample surface. A glassplate is placed directly on top of the oil drops. After 3 minutes, theglass plate is removed and any excess oil blotted off the surface. Thefilm side of the sample is visually inspected for a change in appearanceindicating penetration or staining by the test oil. The oil ratingcorresponds to the highest number oil that does not cause visiblestaining on the film sample side being tested.

Moisture Vapor Transmission Rate Test (MVTR)

The moisture vapor transmission rate for each sample was determined inaccordance with ISO 15496 except that the sample water vaportransmission (WVP) was converted into MVTR moisture vapor transmissionrate (MVTR) based on the apparatus water vapor transmission (WVPapp) andusing the following conversion.

MVTR=(Delta P value*24)/((1/WVP)+(1+WVPapp value)))

Air Permeability

The air permeability for each laminate sample was determined inaccordance with ASTM D737 using the standard pressure drop of 125 Pa,but with the following apparatus modification. An alternate test headarea having an area of 20 cm² was used. The test apparatus used was anFX 3300-20 available from Advanced Testing Instruments of Schwerzenbach,Switzerland. The values, reported in cubic feet per minute, are shown inTable 3.

Water Pick-Up Test

An 8″×8″ square sample is weighed using a calibrated scale that reads tothe nearest 0.1 mg, available from Mettler Toledo of Columbus, Ohio,product item number AG104. The sample is then placed in a hydrostatictester of the sort described in ASTM D751 “Standard Test Methods forCoated Fabrics” section 41 through 49 “Hydrostatic Resistance ProcedureB” with a 4.25″ diameter circle challenge area. The sample is placed sothat the laminate surface that was designed as the outer facing surfaceis challenged by the water, at 0.7 psi for 5 minutes. Take care toensure that no residual water adheres or is absorbed by the back side ofthe sample during placement or removal, as this will alter the reading.After exposure, the sample is removed from the tester and weighed againon the aforementioned scale. All weight gain is assumed to be from waterabsorbed in the challenge area of 4.25″ diameter circle because of thehigh clamp pressure used to hold the sample in place. The water pickupis based on this area using the following calculation to convert tograms per square meter.

Water pick-up=(final sample weight−initial sample weight)/((4.25inch*0.0254 m/inch/2)²*π),

Liquidproof Test (Suter)

Liquidproof testing was conducted as follows. Laminates were tested forliquidproofness by using a modified Suter test apparatus with waterserving as a representative test liquid. Water is forced against asample area of about 4¼-inch diameter sealed by two rubber gaskets in aclamped arrangement. Samples are tested by orienting the sample so thatthe outer film surface of the sample is the surface against which wateris forced. The water pressure on the sample is increased to about 1 psiby a pump connected to a water reservoir, as indicated by an appropriategauge and regulated by an in-line valve. The test sample is at an angle,and the water is recirculated to assure water contact and not airagainst the sample's lower surface. The surface opposite the outer filmsurface of the sample is observed for a period of 3 minutes for theappearance of any water which would be forced through the sample. Liquidwater seen on the surface is interpreted as a leak. A passing(liquidproof) grade is given for where no liquid water is visible on thesample surface within 3 minutes. A sample is “liquidproof” as usedherein, if it passes this test. Samples having any visible liquid waterleakage, e.g. in the form of weeping, pin hole leak, etc. are notliquidproof and fail the test.

Hydrostatic Resistance—Initial

The initial hydrostatic resistance of each sample was determined inaccordance with ASTM D751 “Standard Test Methods for Coated Fabrics.”The pressure was increased until the sample ruptured. The hydrostaticresistance reported was the hydrostatic pressure value at which thesample ruptured. This value was reported in pounds per square inch(psi).

Hook Modified Abrasion

Abrasion was tested as per ASTM D4966, “Standard Test Method forAbrasion Resistance of Textile Fabrics (Martindale Abrasion TesterMethod)” using a Martindale Abrasion test apparatus with the followingmodifications. A 6.25″ diameter circle specimen was placed over thestandard piece of felt on the testing table face up, so the film surfaceof the sample is subject to abrasion challenge. The specimen in thespecimen holder was replaced by a 1.5″ diameter circle of the hook sideof a hook and loop fastener with the hooks facing down so that theychallenge the sample. This material is nylon hook obtainable at partnumber 1509000075 from Norman Shatz Co. of 3570 East Street Road,Bensalem, Pa. 19020 as “Two inch wide Black Hook and Loop”. FIGS. 3 aand 3 b are scanning electron micrographs of an example of the hookmaterial that is suitable for use in this test.

Abrasion movements were conducted at regular intervals with color changeand/or hydrostatic resistance measurements made at the end of eachmovement interval. Initially, the movement interval is 400 movementsuntil 2400 movements are reached. After this, the movement intervaljumped to 800 movements until 9600 movements are reached. After this,the movement interval jumped to 1600 movements for the remainder of thetest. Sample testing for all samples was stopped at 16000 movements.

Color Change after Hook Modified Abrasion

After each abrasion movement interval the sample is removed from theabove described Martindale test table and its performance is evaluated.An L*a*b* reading of the middle of the sample was taken using an X-Ritei1 Basic spectrophotometer (X-Rite World Headquarters in Grand Rapids,Mich. or www.xrite.com). The difference between this “after abrasion”reading and the initial reading taken in the same spot but prior to anyabrasion movements is calculated. To determine the color change at eachabrasion movement interval, the root mean square of this differencevalue is calculated using the equation below.

Color change=((movement L*reading−initial L*reading)²+(movementa*reading−initial a*reading)²+(movement b*reading−initialb*reading)²)^(1/2)

This root mean square of the color change value is reported in units ofdelta E (dE).

Liquidproof (Suter)—After Hook Modified Abrasion

The liquidproofness of each sample after any given abrasion movementinterval was determined using the “Liquidproof Test (Suter)” describedabove. A sample is no longer liquidproof when any visible water leakage,such as weeping, pin hole leak etc., is observed. No further abrasion orliquidproof testing conducted on the sample.

Hydrostatic Resistance After Hook Modified Abrasion

The hydrostatic resistance after abrasion was determined in accordancewith ASTM D751 “Standard Test Methods for Coated Fabrics” with thefollowing exception. Each test specimen was abraded in accordance withthe previously mentioned Hook Modified Abrasion Method, however, sampleswere abraded for 1,000 movements using the hook side of the hookfastener as the abradant. Each specimen was then tested for hydrostaticresistance in accordance with ASTM D 751 oriented so that the outer filmsurface facing the water. These values are reported in pounds per squareinch (psi).

EXAMPLES

Two layer laminates were formed having an outer film surface and aninner textile surface described according to the following examples,

Membrane 1 (M1)

A moisture vapor permeable, microporous polytetrafluoroethylene (PTFE)membrane was produced that was produced from a PTFE resin made accordingto the teachings of U.S. Pat. No. 6,541,589. The PTFE resin comprisedabout 0.5 wt % polyfluorobutylethylene (PFBE) based on the total resinweight, and was processed into an expanded PTFE (ePTFE) membraneaccording to the teachings of U.S. Pat. No. 3,953,566. Properties forthis membrane are detailed in Table 1.

Membrane 2 (M2)

A moisture vapor permeable, microporous PTFE membrane was produced fromPTFE resin and processed into an expanded polytetrafluoroethylene(ePTFE) membrane according to the teachings of U.S. Pat. No. 5,814,405.Properties for this membrane are detailed in Table 1.

Membrane 3 (M3)

A moisture vapor permeable, microporous PTFE membrane was produced fromPTFE resin and processed into an expanded polytetrafluoroethylene(ePTFE) membrane according to the teachings of U.S. Pat. No. 3,953,566.Properties for this membrane are detailed in Table 1.

Membrane (M4)

A moisture vapor permeable, microporous membrane was produced from PTFEresin and processed into an expanded polytetrafluoroethylene (ePTFE)microporous membrane according to the teachings of U.S. Pat. No.3,953,566. The properties for this membrane are detailed in Table 1.

Membrane 5 (M5)

A microporous membrane produced from PTFE resin processed into anexpanded microporous polytetrafluoroethylene (ePTFE) membrane accordingto the teachings of U.S. Pat. No. 3,953,566. The properties of thismembrane are detailed in Table 1.

TABLE 1 Properties of Porous Membranes. Membrane M1 M2 M3 M4 M5Mass/area (g/m²) 20 20 55 18 6 Density (g/cm³) 0.66 0.97 0.54 0.46 0.56Thickness (μm) 30 20 100 39 10 Gurley (s) 21 113 22 10 4 Mean flow pore200 113 285 250 214 diameter (nm) Ball burst load (lbf) 20 28 33 17 5Maximum load 8/19/14 16/27/22 24/29/27 6/13/10 4.0/3.2/3.6 (L/T/average)(N) Modulus (L/T/average) 29/158/94 160/319/240 46/57/51 12/68/4060/22/41 (Mpa) MTS (L/T/average) 55/145/100 117/205/161 64/78/7150/106/78 100/79/90 (Mpa) Toughness 24/20/22 41/42/42 30/23/26 19/13/1614/14/14 (L/T/average) (Mpa)

Textile 1 (T1)

A woven polyester textile was provided that was comprised of yarns andweighing about 80 g/m² available from Milliken & Company (Spartanburg,S.C.; style number 141125.)

Textile 2 (T2)

A woven nylon 6,6 textile was provided that was comprised of yarns andweighing about 50 g/m² available from Milliken & Company (Spartanburg,S.C.; style number 131907.)

Textile 3 (T3)

A knit textile was provided that was comprised of polyester in the formof a flat warp knit having a weight of approximately 38 g/m², from GlenRaven, Inc. (Glen Raven, N.C.; part number A1012.)

Colorization Method 1 (Blue)

After lamination, the ePTFE membrane surface of the two layer laminatewas printed using a blue colored, solvent-based, pigment-containing inkcapable of wetting the ePTFE. The laminate was printed using an Epsonsolvent capable, ink-jet printer to form a colorized outer film surface.

Colorization Method 2 (Red)

After lamination, the ePTFE membrane surface of the two layer laminatewas printed using a red colored, solvent-based, pigment-containing inkcapable of wetting the ePTFE. The laminate was printed using an Epsonsolvent capable, ink-jet printer to form a colorized outer film surface.

Oleophobic Coating 1 (C1)

The colorized, ePTFE outer film surface of the laminate was coated with2-propanol (Sigma-Aldrich Chemical Corporation, St. Louis, Mo.) so thatthe film was completely wet. After wetting, it was immediately (in lessthan about 30 seconds) coated with a fluoropolymer solution, formulatedby mixing about 6.0 g of fluorocarbon (AG8025, Asahi Glass, Japan) inabout 14.0 g of deionized water. The colorized film surface was handcoated with the mixture using a roller to a coating weight ofapproximately 3 g/m². The coated film was cured at 180° C. for 2minutes.

Oleophobic Coating 2 (C2)

The colorized, ePTFE outer film surface of the laminate was renderedoleophobic by coating with about 2.5% solution of Teflon® AF (DuPontFluoropolymers, Wilmington, Del.) in Fluorinert® FC-40 (3M Corporation,Minneapolis, Minn.) solvent. The colorized film surface was hand coatedusing a roller to a coating weight of approximately 3 g/m², and dried at180° C. for about 2 minutes.

Examples 1-14

Laminates were formed comprising an outwardly facing colorized outerfilm surface and a textile.

Laminate samples for Examples 1-14 were constructed using the specificporous membrane and textile detailed in Table 2. The porous film andtextile were laminated together by gravure printing a dot pattern ofmoisture curable polyurethane adhesive onto the membrane surface. Theadhesive was prepared according to the teachings of U.S. Pat. No.4,532,316, covering approximately 35% of the membrane surface. Theadhesive-printed side of the ePTFE membrane was pressed to one side ofthe woven textile in a nip roll and then passed over a heated roll toform a two layer laminate. The moisture cure adhesive was allowed tocure for 48 hours.

The laminates were colorized according to the specific colorization andoleophobic coating methods in accordance to Table 2.

TABLE 2 Description of Laminate Examples. Example Number MembraneTextile Colorization Coating 1 M1 T1 Blue C2 2 M2 T1 Red C1 3 M1 T2 BlueC1 4 M2 T3 Blue C1 5 M2 T3 Blue C2 6 M3 T1 Blue C1 7 M3 T1 Blue C2 8 M2T2 Blue C1 9 M2 T1 Blue C1 10 M2 T1 Blue C2 11 M4 T1 Blue C1 12 M4 T1Blue C2 13 M5 T1 Blue C1 14 M5 T1 Blue C2 16 M4 T2 Blue C1

Laminates were formed that were lightweight, moisture vapor permeable,air permeable, having an oil rating of 5 or greater and low waterpickup, when tested according to the methods described herein. Theresults are reported in Table 3.

To compare the low water pickup of laminates having an outer filmsurface to materials that are liquidproof but having a textile outersurface, a comparative material sample was obtained. Comparative Sample1 was a commercially available material comprising a nylon textile(tightly woven) having a microporous polyurethane on one side and adurable water repellant (DWR) coating on the other side. Comparativesample 1 was tested for water pickup on the DWR side of the sample, andhad a water pickup of about 11 gsm, significantly higher than waterpickup of Examples 1-11 reported in Table 3.

TABLE 3 Laminate Characteristics. Air Water Example Mass/area Oil MVTRpermeability pickup number (g/m²) rating (g/m²/24 hr) (ft³/min) (g/m²) 1112 5 22,550 0.007 2.1 2 122 5 5,010 0.001 1.2 3 96 5 8,040 0.003 3.1 491 6 19,110 0.005 1.1 6 173 6 23,430 0.02 4.1 8 107 5 15,800 0.01 2.9 9144 6 5,630 0.001 2.1 11 151 6 20,990 0.007 6.9 13 114 6 16,200 0.007Leak 16 93 5 4,224 0 14.5 17 66 1 2,806 0 11.7

The laminates were tested to determine the number of abrasion movementsbefore loss of liquidproofness and for hydrostatic resistance before andafter abrasion, as described in the test methods herein. The results arereported in Table 4.

TABLE 4 Laminate Liquidproofness and Hydrostatic Resistance Results.Abrasion Effect on Abrasion Effect Liquidproofness on HydrostaticAbrasion Abrasion Resistance Movements Movements At After Example WithNo Leakage Failure Initial abrasion Number (movements) (movements) (psi)(psi) 1 3600 4400 — — 2 4400 5200 — — 3 3800 4400 — — 4 1400 1800 82 785 — — 80 75 6 9200 9600 52 73 7 — — 59 80 8 11600  12000  — — 9 68007600 130 166 10 — — 131 167 11 1200 1600 115 149 12 — — 130 155 13failed at first  400 95 0 interval 14 — — 135 0 16 16000  * — — 17failed at first  <50 — — interval *Example 16 showed no leakage at 16000movements

The laminate of Example 1 was tested for the durability of the aestheticappearance by testing according to the method for Color Change AfterAbrasion described, herein. After abrasion on the outer film surface,the laminate had a color change of about 8 dE.

Example 15

An outwear jacket having an exterior film surface was constructed usinga simple garment pattern having no pockets or hood, and a full lengthfront zipper (4), as exemplified in FIGS. 1 a and 1 b.

A laminate was constructed comprising an ePTFE outer film surfacesimilar to that of Example 3 except laminated to a knit textile layer,rather than the woven textile of Example 3, by discontinuous adhesiveattachments. An oleophobic coating was applied to the outer filmsurface. The garment sleeves were terminated with elastic cuffs havingadjustable hook and loop tabs. The bottom circumferential hem wasprovided with an elastic draw cord in order to accommodate a range ofwaist sizes.

The jacket was constructed sewing the patterned laminate pieces togetherby orienting the outer film surface to the exterior side of the jacketusing a single needle seam machine having a 65 ball point needle. Thesewing machine included a knife edge which trimmed off any excesslaminate so that the seam could later be sealed using a narrow seamtape. The jacket seams were sealed with a hot-melt seam tape having asufficiently low melt-viscosity such that the adhesive can penetratethrough the knit fabric, contacting the ePTFE membrane to make a watertight seam, using a standard hot-melt seam sealing machine. The seamseal tape was applied to the knit textile side of the jacket laminate.

The back flap along the inside edge of the front zipper was reinforcedwith sheet adhesive, thereby preventing it from being caught in thezipper. The resulting garment was a men's size XL having a total garmentweight of approximately 9.1 ounces.

Example 16

This laminate sample was constructed in the same manner as Examples 1-14using the components listed in Table 2 with the following exception.Before lamination, the membrane, M4, was coated with a partially imbibedmonolithic polyurethane layer according to U.S. Pat. No. 4,969,998. Thepolyurethane coated M4 was laminated such that the uncoated ePTFE sidewas oriented away from the textile, 12. All remaining processes are asdetailed in the description of Examples 1-14.

Example 17

A commercially available two layer laminate consisting of a microporouspolypropylene film bonded to a polypropylene point bonded nonwoven wasused as a reference. This is available under the trade name DriDucks™from Frogg Toggs® (131 Sundown Dr. NW, Arab, Ala. 35016) under partnumber D51204-04. This product was tested with the microporouspolypropylene film as the external surface. This laminate was tested forliquidproofness after abrasion, the results for which are reported inTable 4.

While particular embodiments of the present invention have beenillustrated and described herein, the present invention should not belimited to such illustrations and descriptions. It should be apparentthat changes and modifications may be incorporated and embodied as partof the present invention within the scope of the following claims.

1.-23. (canceled)
 24. An outerwear garment having an abrasion resistantexterior film surface, comprising a textile composite consistingessentially of 1) a first layer consisting essentially of a porousfluoropolymer film comprising a porous fluoropolymer membrane having anaverage ball burst load greater than 17 lb force, the porousfluoropolymer film having a colorized, oleophobic outer film surface,and an inner film surface opposite the outer film surface; and 2) secondlayer consisting essentially of a knit layer bonded to the porousfluoropolymer film by adhesive attachment adjacent to the inner filmsurface; wherein the outerwear garment is assembled so that thecolorized, oleophobic outer film surface is the garment exterior filmsurface, the textile composite has a moisture vapor transmission rategreater than 4000 g/m²/24 hours, and the textile composite is abrasionresistant remaining durably water proof after more than 1400 abrasionmovements on the outer film surface.
 25. The outerwear garment of claim24, wherein the porous fluoropolymer film comprises a membranecomprising polytetrafluoroethylene (PTFE).
 26. An outerwear garmenthaving an abrasion resistant exterior film surface, comprising a garmentexterior film surface, and a laminate comprising 1) a porousfluoropolymer film having an abrasion resistant, colorized outer filmsurface, and inner film surface opposite the outer film surface, and anoil rating greater than 2, comprising a porous fluoropolymer membranehaving an average maximum load in the transverse and longitudinaldirection greater than 10 N, and 2) a knit or woven textile layer bondedto the porous fluoropolymer film by attachment adjacent to the innerfilm surface; wherein the laminate has a mass per area less than 150g/m², and the outerwear garment is assembled so that the outer filmsurface of the laminate is the garment exterior film surface.
 27. Theouterwear garment of claim 26 wherein the porous fluoropolymer membranecomprises polytetrafluoroethylene (PTFE).
 28. The outerwear garment ofclaim 26 wherein the porous fluoropolymer membrane is microporous. 29.The outerwear garment of claim 26 wherein the porous fluoropolymermembrane comprises expanded PTFE (ePTFE).
 30. The outerwear garment ofclaim 26 wherein the porous fluoropolymer membrane comprises ePTFEcomprising perfluorobutylene (PFBE) comonomer.
 31. The outerwear garmentof claim 26 wherein the porous fluoropolymer membrane has an averagemaximum load greater than 12 newtons (N).
 32. The outerwear garment ofclaim 26 wherein the porous fluoropolymer membrane has an averagemodulus in the longitudinal and transverse greater than 40 MPa.
 33. Theouterwear garment of claim 26 wherein the porous fluoropolymer membranehas an average modulus greater than 70 MPa.
 34. The outerwear garment ofclaim 26 wherein the porous fluoropolymer membrane has a mass per arealess than 80 g/m².
 35. The outerwear garment of claim 26 wherein theporous fluoropolymer membrane has a mass per area less than 50 g/m². 36.The outerwear garment of claim 26 wherein the porous fluoropolymermembrane has a mass per area between 19 g/m² and 60 g/m².
 37. Theouterwear garment of claim 26 wherein the porous fluoropolymer membranehas a mass per area greater than 10 g/m².
 38. The outerwear garment ofclaim 26 wherein the porous fluoropolymer membrane has a thickness lessthan 120 um.
 39. The outerwear garment of claim 26 wherein the porousfluoropolymer membrane has a thickness less than 35 μm.
 40. Theouterwear garment of claim 26 wherein the laminate is liquidproof afterabrasion on the outer film surface.
 41. The outerwear garment of claim26 wherein the textile is a knit, and the laminate is liquidproof aftermore than 1400 abrasion movements on the outer film surface.
 42. Theouterwear garment of claim 26 wherein the textile is a woven, and thelaminate is liquidproof after more than 2000 abrasion movements on theouter film surface.
 43. The outerwear garment of claim 26 wherein thelaminate has a water pick up value less than or equal to 10 g/m². 44.The outerwear garment of claim 26, further comprising a discontinuouscoating in the form of particulates or discrete elements to providefurther abrasion resistance.
 45. The outerwear garment of claim 44,where the coating of discrete materials comprises a material selectedfrom polyurethane, epoxy, silicone or fluoropolymers.
 46. An outerweargarment having an abrasion resistant, low water pickup exterior filmsurface, comprising a garment exterior film surface, and a laminatecomprising 1) a porous polymer film having an abrasion resistant,colorized outer film surface, and inner film surface opposite the outerfilm surface, and an oil rating greater than 2, comprising a membranehaving an average maximum load in the transverse and longitudinaldirection greater than 10 N, and 2) a knit or woven textile layer bondedto the porous polymer film by attachment adjacent to the inner filmsurface; the laminate having an MVTR greater than 4000 g/m²/24 hours anda mass per area less than 150 g/m², wherein the outerwear garment isassembled so that the outer film surface of the laminate is the garmentexterior film surface having a water pickup of less than 10 g/m².47.-52. (canceled)